Quaternary ammonium salts and process of preparing them



may be interrupted by Patented Aug. 26, 1947 QUATEBNARY PROCESS OF Gerhard Balle,

Rosenbacli, Wiesbaden, Frankfort-on-tlie-Main, Germany, ass! by mesne assignments, to General Aniline &

Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 11, No. 273,042. In Germany May 2 Claims. (or. 260-295) 1 The present invention relates to quaternary ammonium salts and to a process of preparing them.

We have found that valuable quaternary ammonium salts are obtainable by converting esterlike constituted compounds'having the formula RXCH2-OCOR2H&1 wherein R stands for an aliphatic, aliphatic-cycloaliphatic or aralis PATENT OFFICE AMIMONIUM SALTS AND PREPARING THEM Frankfort-on-the-Main, Johann phatic radical of at least 12 carbon atoms which heteroatoms; X means oxygen or sulfur; R2 represents a low molecular aliphatic hydrocarbon radical which may be substituted by halogen, and Hal means halogen into quaternary ammonium salts. This conversion into quaternary ammonium salts is carried out by causing the starting materials corresponding with the above-indicated formula to react with tertiary aliphatic or heterocyclic bases.

The ester-like constituted compounds of the above-indicated formulae used as starting materials are prepared according to the process of U. S. Patent No. 2,283,764, issued May 19, 1942, for Ester-like condensation products and a process Of preparing them in the name of Johann Rosenbach and Gerhard Balle.

Halogen-substituted esters which may be used as starting materials for the present invention are, for instance: the products of the reaction of salts of chloracetic acid,'dichloracetic acid, bromoacetic acid, alphaor beta-chloropropionic acid with halogen-methyl ethers of monoor polyhydric alcohols, such as dodecanols, octadecanols, oleyl alcohol, montan alcohols, resin alcohols and Y the hydrogenation products thereof, octadecanediol, dichlorooctadecane-diol, octadecyl-monoglycol ether, para-butylphenyl-butanol, octadecylphenyldiglycol ether, naphthene alcohols. The corresponding halogen-methyl compounds may be made, for instance, as described in British specification No. 394,196.

Furthermore, there may be named the esterlike constituted compounds prepared by the reaction of salts of halogenated acids with the halogen-methyl compounds of monoor polyhydric mercaptans, such as dodecylmercaptan, octadecylmercaptan, which may be produced in a manner analogous to that of the halogen-methyl ethers already named.

There are also suitable the products obtainable from salts of the above-mentioned halogenated acids and from the halogen-methyl compounds of carboxylic acid amides or carbamic acid esters, for instance. lauric acid amide, stearic acid amide, oleic acid amide, acetic acid-N-octadecyl-amide, butyric acid-N-dodecyl amide, stearic acid methylamide, montanic acid amide, resinic acid amides, the amides of col ester.

this nitrogen atom is the member of an unsatuthe carboxylic acids obbutylphenylbutyric scribed in French Patents Nos. 818,438, and

- atoms and containing for a short time or and Ludwig Ortlmer,

1939, Serial 14, 1938 tainable by oxidation of paraflin or by similar processes which have at least 12 carbon atoms, furthermore, dichlorostearic acid amide, ricinoleic acid methylamide, iso-octylphenoxyacetic acid amide, isododecylcyclohexyl-oxyacetic acid amide, tributylphenylacetic acid-N-butylamide, paraacid amide, carbamic acid dodecyl ester, N-methylcarb'amic acid octadecyl ester, carbamic acid iso-dodecyl phenyl ester, N-methylcarbamic acid iso-dodecylcyclohexylgly- The corresponding halogen-methyl compounds may be prepared, for instance, as de- Besides there are appropriate the reaction products of the salts of halogenated carboxylic acids with halogen-methyl compounds obtainable by causing a compound having at least 12 carbon nitrilo-group to react with formaldehyde in the presence of hydrogen halide.

Of esters containing basic nitrogen which may be transformed into quaternary ammonium salts, there may be named, for instance,t-he esterlike compounds obtained by reaction of the abovenamed halogen-methyl compounds with salts of dimethylamino-acetic acid, piperidino-acetic acid, alphaand beta-diethylaminopropionic acid.

The procedure is of the two reaction components necessary for the preparation of the ammonium salts is heated it is allowed to stand for a prolonged time at ordinary temperature the simultaneous application, of a solvent being advantageous in some cases. The product precipitates in most cases in a crystalline form and is separated from the solvent.

The quarternary ammonium salts thus produced correspond with the general formula R.X.CH1.Q C O Rz-IITEZ Hal phatic hydrocarbon radicals are attached or that rated heterocyclic ring system or the member of a saturated heterocyclic ring system in which latter case still an aliphatic hydrocarbon radical is'bound at the nitrogen atom.

The new products are generally solid bodies which are soluble or capable of being dispersed in water and may be used in the textile industry for rendering fibrous material water-repellent in which case it is necessary to subject the imthe following: The mixture a halogen atom and Z means 4 pregnated textile material to a heat-treatment. mixed with 150 parts of pyridine and the precipi- They may be used either per se or in admixture tated crystalline mass is filtered with suction with other products having a similar action, such after 3 .days' standing. In order to remove the as fatty alcohol sulfonates, fatty acid condensaexcess-of pyridine it is washed with acetone. A tion products, alkylated naphthalenesulfonic 5 brownish product is obtained which dissolves in acids or the like. water to a clear solution.

The following examples serve to illustrate the (8) 25 parts of the substance obtained from invention, but they are not intended to limit it octadecyl-chloromethyl ether and sodium dithereto; the parts are by weight: methyl-aminoacetate are dissolved in 30 parts of (l) 25 parts of the product of the reaction of 10 ethylene chlorhydrin and the mixture is allowed dodecyl-chloromethyl ether and sodium chlorto stand for 3 days at ordinary temperature.

acetate are heated to boiling for 1 hour with The precipitated colorless crystalline mass is parts of dimethylamino-ethyl-methyl ether and filtered with suction and dried at 30 C. under 150 parts of benzene. The solvent is then elimreduced pressure.

inated at 50 C. to 60 C. under reduced pressure. 15 (9) 80 parts of an ester of the formula The residue forms a, soft, brownish mass which CiaHai.O.CHi.0.CO.CHCli are dissolved in 100 gives with water clear, well-foaming solutions. parts of benzene and 16 part of Py i are (2) 150 parts of the product of the reaction of added. The whole is allowed to stand for 3 days hexadecyl-chloromethyl ether with sodium chlorat room temperature. Then the benzene is acetate are dissolved in 350 parts of pyridine. 20 distilled under reduced pressure. There remains The mixture is allowed to stand for about 3 days a feebly brown colored product which dissolves at ordinary temperature, the precipitated crysin water to a clear solution. The ester used as talline mass is filtered with suction and washed starting material is obtainable by condensing with acetone. The compound obtained is a feebly octadecyl-choromethyl ether with sodium colored body which is soluble in water to a clear dichloroacetate. solution. We claim:

(3) Asolution of 20 parts of trimethylainine in 1. The process of preparing quaternary am- 150 parts of benzene is mixed with a mixture of monium salts which comprises reacting an ester- 40 parts of the ester prepared from octadecyllike constituted compound of the general formula chloromethyl ether and sodium chloracetate, and x 100 parts of benzene. The whole is allowed to stand at ordinary temperature for about 40 hours, wherein R stands for a radical of at least 12 the precipitated product is filtered with suction carbon atqms -f f from h group consisting and Subsequently washed with benzene The of aliphatic, ahphatic-cycloahphatic, and aralicompound is a colorless body which is readily phatic radicals which radicals are interrupted by uble mwaten hetero atoms in their carbon structures, X stands (4) 308 parts of the ester obtained from octafor a member of the group s of oxygen decyl-chloroinethyl ether and sodium chloraceand sulfur R2 stands for member of the group tate are dissolved, while gently heating in 175 consisting of low molecular aliphatic hydrocarbon parts of pyridine and allowed to Stand for 3 days 40 radicals and low molecular aliphatic hydrocarbon at ordinary temperature. The crystalli mass. radicals substituted by halogen, and Hal means obtained isstirred with acetone, filtered with suchalogen with a tertiary base of the group tion and washed with acetone The brownish sisting of aliphatic and heterocyclic bases. product dissolves in hot water to a clear solution. The quaternary ammonium salts of the (5) 30 parts of the product of reaction of dogeneral decyl-chloromethyl sulfide and sodium alpha- R XCH2OCOB2NEZ chloropropionate are boiled for some time toa1 5: 3:3 2&3, gg gzg i gi 25222221? 39 wherein R stands for a radical of at least 12 zene is then distilled at 50 0. under reduced 50 l amms selectid mm 3 gmup ns1stmg pressura of aliphatic, aliphatic-cycloaliphatic, and araliphatic radicals which radicals are interrupted by $2 22? fig g if gfisggg 1233 2 333 hetero atoms in their carbon structures, X stands P ig (heaved, While geefly heating, 231311.311; siai di i33fiti3ti $2553; :L xgig g 231223 agi g zg g 1S t 5 consisting of low molecular aliphatic hydrocarnsatio 1 com late th h mt d {K bon radicals and low molecular aliphatic hydron s D 8W 0 s ere W1 carbon radicals substituted by halogen, Hal means tion and washed with acetone. A nearly colorless halogen and NEZ stands for a member f the body remains on the filter which dlSSOlVeS in 1101; grou on i ting of tertiary aliphatic amines and Watertertiary heterocyclic bases.

(7) 60 parts of the reaction product obtained 1 GERHARD BALLE. from the chloromethyl compound of carbamic JOHANN ROSENBACH. acid octadecyl ester and sodium chloracetate are LUDWIG ORTHNER. 

